WO2000034356A1 - Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung - Google Patents

Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung Download PDF

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Publication number
WO2000034356A1
WO2000034356A1 PCT/EP1999/009069 EP9909069W WO0034356A1 WO 2000034356 A1 WO2000034356 A1 WO 2000034356A1 EP 9909069 W EP9909069 W EP 9909069W WO 0034356 A1 WO0034356 A1 WO 0034356A1
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WO
WIPO (PCT)
Prior art keywords
equivalent
blocked
formaldehyde
triazole
polyisocyanates
Prior art date
Application number
PCT/EP1999/009069
Other languages
German (de)
English (en)
French (fr)
Inventor
Eberhard König
Hans-Ulrich Meier-Westhues
Thomas Klimmasch
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE1998156412 external-priority patent/DE19856412A1/de
Priority claimed from DE1998156968 external-priority patent/DE19856968A1/de
Priority to AT99959318T priority Critical patent/ATE226221T1/de
Priority to CA002353381A priority patent/CA2353381A1/en
Priority to BR9915958-9A priority patent/BR9915958A/pt
Priority to JP2000586797A priority patent/JP2002531651A/ja
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU16540/00A priority patent/AU1654000A/en
Priority to US09/857,087 priority patent/US6559264B1/en
Priority to DE59903122T priority patent/DE59903122D1/de
Priority to EP99959318A priority patent/EP1141070B1/de
Priority to KR1020017007010A priority patent/KR20010093802A/ko
Publication of WO2000034356A1 publication Critical patent/WO2000034356A1/de
Priority to HK02104522.7A priority patent/HK1042907A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/006—Polymeric products of isocyanates or isothiocyanates with aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
    • C09K15/22—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen containing an amide or imide moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to blocked polyisocyanate crosslinking agents, their production and use in IK stoving lacquers, in particular OEM clear lacquers (original equipment material, first lacquering).
  • blocked polyisocyanates are used as improving additives in 1-component stoving lacquers in automotive painting. With blocked polyisocyanates, demanding requirements for improved paint properties can be met relatively well. Other properties, such as a low baking temperature up to max. 140 ° C or low thermal yellowing when overburning, on the other hand, cannot be achieved with all available raw materials.
  • the most important technical lacquer polyisocyanates are based on 1,6-diisocyanato-hexane (HDI).
  • Blocking agents for polyisocyanates available on an industrial scale are malonic esters and 1,2,4-triazole, if deblocking temperatures of up to 140 ° C. are taken into account.
  • the combination of HDI based polyisocyanates with Malonester or 1,2,4-triazole, or, as the following comparative example demonstrates, with a mixture of Malonester / 1 J, 4-tri ol *, does not lead to a useful shelf-stable and liquid Lackvernetzer because crystallize these products.
  • the tendency towards crystallization of malonic ester-blocked HDI polyisocyanates is already known from EP-A 600 314, that of triazole-blocked polyisocyanates from EP-A 654 490 and 741 157.
  • the object of the invention was to modify HDI-based polyisocyanates mixed-blocked with malonic ester and 1,2,4-triazole in such a way that liquid crosslinkers for IC baking lacquers which do not crystallize in solvents result. This problem was solved with the blocked polyisocyanates described below.
  • the invention relates to aliphatic and / or cycloaliphatic polyisocyanates, the isocyanate groups of which
  • blocked (reacted) are present, characterized in that they contain 0.05-1.0 mol of formaldehyde in the incorporated form, based on 100 equivalent% of blocked NCO groups.
  • the invention also relates to a process for the preparation of the non-crystallizing blocked polyisocyanates according to the invention from
  • the non-crystallizing blocked polyisocyanates according to the invention can preferably have a level of stabilizers against thermal yellowing of
  • Such stabilizers are e.g. known from EP-A 829 500.
  • the invention also relates to the use of the blocked polyisocyanates according to the invention as crosslinking agents for organic polyhydroxyl compounds in polyurethane stoving lacquers, for example for automotive clear lacquers.
  • the content of formaldehyde is essential to the invention for the polyisocyanate crosslinking agents claimed.
  • the formaldehyde surprisingly shows two modes of action: First, it prevents the crystallization of the blocked polyisocyanates, especially when the polyisocyanate component is based on HDI. On the other hand, it increases the resistance of the blocked polyisocyanates to thermal yellowing.
  • Per 100 equivalent% blocked polyisocyanate 0J to 0.4 mol of paraformaldehyde are preferably used and reacted by means of a catalyst, such as Na methylate. This is approximately 0.8 to 5.0% by weight of formaldehyde, based on blocked polyisocyanate.
  • the polyisocyanate component is optionally mixed with a little solvent, e.g.
  • 1-methoxy-2-propyl acetate (MPA), initially charged at approx. 50 ° C, the CH-acidic ester, e.g. Malonic ester, is added as a mixture with about 2% of a 30% Na methylate solution and reacted at 70-90 ° C until the calculated NCO content. Then the calculated amount of 1,2,4-triazole, dissolved in further MPA, is added and the mixture is reacted at about 90 ° C., so that no more NCO groups can be detected. The batch is cooled to about 45 ° C.
  • the CH-acidic ester e.g. Malonic ester
  • the polyisocyanates on which the blocked polyisocyanates according to the invention are based are known lacquer polyisocyanates with aliphatic and / or cycloaliphatic and / or aromatically bound isocyanate groups and an isocyanate content of 7 to 30, preferably 12 to 25,% by weight.
  • HDI 1,6-diisocyanatohexane
  • IPDI 5-trimethyl-5-isocyanatomethyl-cyclohexane
  • H 12 MDI or Desmodur W® / Bayer AG lacquer polyisocyanates containing allophanate and / or uretdione groups based on 1,6-diisocyanatohexane (HDI), l-isocyanato-3J, 5-trimethyl-5-isocyanatomethyl-cyclohexane (I
  • asymmetrically trimerized lacquer polyisocyanates based on 1,6-diisocyanatohexane which in addition to isocyanurate also have iminooxadiazinedione groups, can be used as polyisocyanate components, as described, for example, in EP-A 798 299.
  • Polyisocyanates based on other isocyanates such as e.g. 1,4-diisocyanato-butane, 2,4- or 2,6-diisocyanato-1-methyl-cyclohexane, 2,5- and / or 2,6-bis-isocyanato-norbornane, 3- and / or 4- Isocyanatomethyl-1-methylcyclohexane, 1,4-bis (2-isocyanato-prop-2-yl) benzene, 1J-diisocyanatomethylbenzene, 1, 3- or 1,4-bis-isocyanatomethylcyclohexane can be used.
  • 1,4-diisocyanato-butane 2,4- or 2,6-diisocyanato-1-methyl-cyclohexane
  • 2,5- and / or 2,6-bis-isocyanato-norbornane 3- and / or 4- Isocyanatomethyl-1-methylcyclohex
  • isocyanurate group-containing polyisocyanates based on 1,6-diisocyanatohexane are very particularly preferred as the polyisocyanate component.
  • CH-acidic esters come on the one hand as the blocking component
  • 1,2,4-triazole is used in this mixed blocking. The latter can be obtained on an industrial scale from 1 mol of hydrazine hydrate and at least 2 mol of formamide.
  • the CH-acidic esters or triazole can be used in amounts of
  • Amounts of up to 50 equivalent%, preferably up to 20 equivalent%, can also be used as additional blocking agents: oximes, such as e.g. Butanone oxime, secondary amines, e.g. Diisopropylamine, NH-acidic heterocycles, e.g. Imidazole or 3,5-dimethylpyrazole or lactams, e.g. ⁇ -caprolactam.
  • oximes such as e.g. Butanone oxime, secondary amines, e.g. Diisopropylamine, NH-acidic heterocycles, e.g. Imidazole or 3,5-dimethylpyrazole or lactams, e.g. ⁇ -caprolactam.
  • the stabilizers known from EP-A 0 829 500 can be used as additional stabilizing components.
  • the readily accessible hydrazide of the formula (Ia) which is readily accessible by adding hydrazine hydrate to 2 mol of propylene carbonate
  • the first-mentioned stabilizer is preferably 3 to 6% by weight, the latter preferably 0.5 to 1.5% by weight, in each case based on blocked
  • Solvents which are known from polyurethane chemistry and which are inert to NCO groups, for example 1-methoxy-2-propyl acetate, solvent naphta 100 or butyl acetate, can be used. If the NCO groups are blocked, alcohols, e.g. Isobutanol to enable transesterification with the alcohol residues of the blocking agent.
  • This mixed-blocked polyisocyanate is stabilized with 3.0% of formaldehyde, based on the solids content of the blocked polyisocyanates.
  • the ratio of the blocking agents for malonic ester: triazole 40:60 equivalent%, based on 100 equivalent% of NCO groups.
  • HDI 1,6-diisocyanatohexane
  • Polyisocyanate and methoxypropyl acetate are introduced and heated to approx. 50 ° C.
  • Example 2 This example is similar in type and amount to Example 1 except that the modification of the blocked polyisocyanate with formaldehyde is omitted. The result is a product which begins to crystallize after one week of storage at room temperature. This blocked polyisocyanate can therefore not be used in storage-stable IC lacquer formulations.
  • This mixed-blocked polyisocyanate is stabilized at 2.1%, based on the solids content of the blocked polyisocyanate. There are also two more
  • Stabilizers (cf. EP-A 829 500 A2) mixed in the blocked polyisocyanate solution, namely 2.0% of a hydrazide which has already been explained and 1.0% of a HALS amine.
  • NCO content of approx. 21%, a viscosity at 23 ° C of approx. 3,000 mPas and a functionality of approx. 3.5
  • Solids content 70% blocked NCO content: 8.8% viscosity (23 ° C): approx.5,000 mPas Appearance: clear, Hazen 60
  • the polyisocyanate and methoxypropyl acetate are presented. At about 50 ° C and with stirring, the mixture of diethyl malonate is carried with about 2%, ie. H.
  • the crosslinker according to Example 3 becomes one with the following components
  • This clear lacquer is applied to test panels that are coated with a commercially available white basecoat, e.g. from Spies & Hecker / Cologne, are applied in a wet layer thickness of approx. 120 to 150 ⁇ m and, as explained in the table below, baked and tested.
  • a commercially available white basecoat e.g. from Spies & Hecker / Cologne
  • Pendulum damping (vibrations) 0 143 (s) 200

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Steroid Compounds (AREA)
  • Liquid Crystal Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Colloid Chemistry (AREA)
PCT/EP1999/009069 1998-12-07 1999-11-24 Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung WO2000034356A1 (de)

Priority Applications (10)

Application Number Priority Date Filing Date Title
KR1020017007010A KR20010093802A (ko) 1998-12-07 1999-11-24 말론산 에스테르/트리아졸 혼합물로 차단된ｈｄｉ삼량체/포름알데히드 안정화
EP99959318A EP1141070B1 (de) 1998-12-07 1999-11-24 Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung
CA002353381A CA2353381A1 (en) 1998-12-07 1999-11-24 Malonic acid ester/triazole mixed blocked hdi trimer/formaldehyde stabilization
BR9915958-9A BR9915958A (pt) 1998-12-07 1999-11-24 Estabilização, mediante formaldeìdo/hditrimesato em bloco misto com éster de ácido malÈnico/triazol
JP2000586797A JP2002531651A (ja) 1998-12-07 1999-11-24 マロン酸エステル／トリアゾール混合されたブロック化ｈｄｉトリマー／ホルムアルデヒドの安定化
AT99959318T ATE226221T1 (de) 1998-12-07 1999-11-24 Malonester/triazolmischblockiertes hdi- trimerisat/formaldehydstabilisierung
AU16540/00A AU1654000A (en) 1998-12-07 1999-11-24 Malonic acid ester/triazole mixed blocked hdi trimer/formaldehyde stabilization
US09/857,087 US6559264B1 (en) 1998-12-07 1999-11-24 Malonic acid ester/triazole mixed blocked HDI trimer/formaldehyde stabilization
DE59903122T DE59903122D1 (de) 1998-12-07 1999-11-24 Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung
HK02104522.7A HK1042907A1 (zh) 1998-12-07 2002-06-18 用丙二酸酯和三唑混合封閉的、含甲醛的1，6-二異氰酸根絡環己烷三聚體的穩定化方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE1998156412 DE19856412A1 (de) 1998-12-07 1998-12-07 Verfahren zur Koagulation wäßriger PUR-Dispersionen die reaktives oder nachvernetzbares Polyurethan dispergiert enthalten, so erhaltene Produkte und deren Verwendung
DE19856412.0 1998-12-07
DE19856968.8 1998-12-10
DE1998156968 DE19856968A1 (de) 1998-12-10 1998-12-10 Malonester/Triazolmischblockiertes HDI-Trimerisat/Formaldehydstabilisierung

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WO2000034356A1 true WO2000034356A1 (de) 2000-06-15

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PCT/EP1999/009068 WO2000034352A1 (de) 1998-12-07 1999-11-24 Verfahren zur koagulation wässriger pur-dispersionen, die reaktives oder nachvernetzbares polyurethan dispergiert enthalten, so erhaltene produkte und deren verwendung
PCT/EP1999/009069 WO2000034356A1 (de) 1998-12-07 1999-11-24 Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung

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US (2) US6559264B1 (pt)
EP (2) EP1141070B1 (pt)
JP (2) JP4916048B2 (pt)
KR (2) KR20010093802A (pt)
CN (2) CN1156505C (pt)
AT (2) ATE253090T1 (pt)
AU (2) AU1385800A (pt)
BR (2) BR9915981B1 (pt)
CA (2) CA2353412C (pt)
DE (2) DE59907571D1 (pt)
ES (2) ES2211233T3 (pt)
HK (2) HK1042907A1 (pt)
HU (1) HUP0104571A3 (pt)
ID (1) ID30165A (pt)
IL (2) IL142924A0 (pt)
PL (1) PL200857B1 (pt)
PT (1) PT1141070E (pt)
TR (1) TR200101655T2 (pt)
WO (2) WO2000034352A1 (pt)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002055577A1 (en) * 2001-01-12 2002-07-18 Baxenden Chemicals Limited Mixed-blocked polyisocyanates and uses thereof

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